CN104532308B - A kind of leveling agent for acid copper plating and application thereof - Google Patents
A kind of leveling agent for acid copper plating and application thereof Download PDFInfo
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- CN104532308B CN104532308B CN201410845771.0A CN201410845771A CN104532308B CN 104532308 B CN104532308 B CN 104532308B CN 201410845771 A CN201410845771 A CN 201410845771A CN 104532308 B CN104532308 B CN 104532308B
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- Prior art keywords
- leveling agent
- hole
- acid
- copper
- copper plating
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Classifications
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/38—Electroplating: Baths therefor from solutions of copper
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
- C25D7/04—Tubes; Rings; Hollow bodies
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/40—Forming printed elements for providing electric connections to or between printed circuits
- H05K3/42—Plated through-holes or plated via connections
Abstract
The invention discloses a kind of leveling agent for acid copper plating and application thereof.The leveling agent is the polymer with thiadiazoles drone salt construction unit, its structural formula such as formula（1）Shown：（1）Wherein, selected from alkyl or the replacement alkyl of 0 10 carbon atoms, n is the integer not less than 2 to R.Used as the leveling agent of sour copper electroplating bath, for acid electroplating, blind hole filling is not in space to a kind of polymer with thiadiazoles drone salt construction unit that the present invention is provided, and amount of recess is with respect to existing conventional planarization agent（As Janus green）Significantly reduce, the electroplates in hole shows good dispersibility, y/x value is all higher than 0.8, can more ideally realize the electroplates in hole and blind hole is filled while electroplating technology.
Description
Technical field
The present invention relates to a kind of acid electroplating additive, and in particular to a kind of leveling agent for acid copper plating and its
Purposes.
Background technology
Currently, electronic product constantly develops towards miniaturization and lightening direction, and this is for the reliability of printed wiring board
Property is put forward higher requirement.The reliability of printed wiring board function is heavily dependent on sour copper electroplating technology, i.e. through hole
Plating and the quality of blind hole fill process.In the past acid copper electroplating technology be laser drill → blind hole plating fill out copper → machine drilling →
The electroplates in hole；Through hole and blind hole constrain production capacity respectively through electroplating work procedure twice, and improve production cost.For solving these
Problem, had developed the electroplates in hole in recent years and blind hole is filled while electroplating technology.If however, use being filled to mesh with blind hole
Electroplating bath carry out the electroplates in hole, can cause through hole corner copper coating thickness abnormity thin, so as to easily produce chink line,
So may not apply to the electroplates in hole；If the electroplating bath for the purpose of the electroplates in hole carries out blind hole filling, blind hole can be caused
The copper coating lower thickness of inner bottom part, it is difficult to effectively carry out blind hole filling.Therefrom it is not difficult to find out, present in sour copper electroplating bath
Organic substance as additive is realized avoiding hole, substrate surface inside uniform copper metal deposit, blind hole for through hole inside
On avoid pin hole and raised wait for most important.
Accelerator can typically be used in acid copper plating bath（Or referred to as accelerator, brightener）, inhibitor（Or be referred to as carrying
Agent, wetting agent）, three kinds of additives of leveling agent.For from electroplating principle, in the electroplates in hole and blind hole filling while electroplating technology
In, accelerator provides Active Growth position to change nucleation process by promoting the charge transfer process on copper interface；Inhibitor
Uniformly adsorb on cathode surface, increase deposition overpotential；Leveling agent selective absorption at high potential position, so as to suppress this
The coating deposition at position.Accelerator diffusion velocity than very fast, and inhibitor and leveling agent diffusion velocity slow；And due to base
Material surface compared with blind via bottom or through hole central part exist higher potential cause the absorption of most of leveling agent in substrate surface and
Aperture position；These factors can suppress substrate surface, and especially suppression aperture side surface upper part separates out copper coating so that diffusion rate
Fast accelerator accelerates deposition copper coating in blind via bottom and through-hole side wall, finally realizes the electroplates in hole and blind hole filling while electricity
Plating.Leveling agent rejection ability is too strong, and it is thin singularly to easily cause openings thickness of coating, so as to easily cause chink line.And
It is raised that the diffusion rate of leveling agent easily causes layers of copper above blind hole filling metapore excessively slowly.
Therefore, need badly and will develop a kind of the electroplates in hole and blind hole of being used for and fill while the leveling agent of electroplating technology.
Content of the invention
It is an object of the invention to provide a kind of additive, which can be used as the leveling agent of acid copper plating electroplate liquid, can be full
Sufficient the electroplates in hole and blind hole filling are while electroplating technology is required.
For reaching above-mentioned purpose, the invention provides a kind of leveling agent for acid copper plating, the leveling agent be with
The polymer of thiadiazoles drone salt construction unit, its structural formula such as formula（1）Shown：
（1）
Wherein, selected from alkyl or the replacement alkyl of 0-10 carbon atom, n is the integer not less than 2 to R.
Above-mentioned acid copper plating composition, wherein, R is selected from the alkoxyl of 2-8 carbon atom.
Above-mentioned acid copper plating composition, wherein, R is selected from the alkyl of 0-5 carbon atom.
Above-mentioned acid copper plating composition, wherein, R is selected from the alkyl of the hydroxyl of 1-4 carbon atom.
Present invention also offers the purposes of above-mentioned leveling agent, the leveling agent can be used as the through hole electricity in printed wiring board
Plating and blind hole filling are while electroplate.
Present invention also offers a kind of acid copper plating copper electroplating liquid composition, which includes copper ion source, electrolyte, rush
Enter agent, inhibitor, wherein, said composition also includes at least one above-mentioned leveling agent.
In electroplate liquid, solvable any copper ion is applicable.Suitable copper ion includes, but are not limited to：Sulfuric acid
Copper, copper chloride, copper nitrate, sulfamic acid copper, copper methanesulfonate.Copper sulphate and copper methanesulfonate are preferred.Can also use
The mixture of copper ion source.In copper electroplating liquid, the content of copper ion is typically in 30-60g/L, preferably 40-50g/L.These copper ions
Salt is commercially available and can be without being further purified.
The acidic electrolyte bath being suitable in electroplate liquid includes, but are not limited to：Sulfuric acid, acetic acid, pyrovinic acid.Sulfuric acid is excellent
Choosing.In copper electroplating liquid, acid content is typically in 30-150g/L, preferably 50-100g/L.Electrolyte includes source of halide.Excellent
The source of halide of choosing is chlorion, is typically added in acid copper plating solution using copper chloride or hydrochloric acid.In electroplate liquid halogen from
The concentration of son is in 10-100ppm, more preferably preferably 30-80ppm, 50-60ppm.These electrolyte be commercially available and
Can be without being further purified.
Electroplate liquid according to the present invention includes accelerator further.This accelerator be well known to a person skilled in the art.
Representational accelerator is the compound containing sulfide or sulfonic acid group, the compound preferably being selected from shown in following formula (2)-(5)
One or more.
（2）
（3）
（4）
（5）
Selected from hydrogen atom and alkali metal, selected from the integer of 1-8, b, c are independently selected from 0 or 1 to a to wherein M.
Some specific suitably accelerator include such as sodium polydithio-dipropyl sulfonate, 3-sulfydryl-1-propane sulfonic acid sodium.
In electroplate liquid, the content of accelerator is preferably from 0.5-100ppm, the more preferably content of accelerator from 0.5-10ppm, even more preferably from from
1-4ppm.If the content of accelerator is less than 0.5ppm in acid copper plating solution, it is difficult to ensure that substrate surface produces bright coating, so as to
The problems such as producing copper powder, pin hole.
Copper electroplating liquid used in the present invention alternatively includes inhibitor.The preferred embodiment of inhibitor has following（6）-
（11）Described structural formula, but it is not limited to these.
（6）, wherein a is the integer of 10-500；
（7）, wherein a is the integer of 10-500；
（8）,
Wherein a, b, c are separately selected from the integer of 10-100；
（9）,
Wherein a, b, c are separately selected from the integer of 10-100；
（10）, wherein a, b divide
Not independently selected from the integer of 10-100；
（11）, wherein n is selected from the integer of 10-500.
Inhibitor used in the present invention can be a kind of or their two or more mixture.Inhibitor
Addition is generally 50-1500ppm, preferably 200-800ppm.If the concentration of inhibitor is less than 50ppm, meeting in electroplate liquid
Reduce the wetting effect of plating solution, so as to a large amount of pin holes be produced in coating surface.
Present invention also offers a kind of preparation method according to above-mentioned leveling agent, the method be with 2,5- diaminourea thiophene two
Azoles, dicarboxylic acid compound form amide polymer intermediate, then the aminoalkyl through dimethyl suflfate to intermediate for raw material
Make.The concretely comprising the following steps of the method：Step 1,2,5- diaminourea thiadiazoles and dicarboxylic acid compound are dissolved in water, and are being stirred
Mix down and be warming up to 150-200oC, is incubated 5-10 hour, then naturally cools to room temperature；Step 2, by dimethyl suflfate and methyl alcohol
It is added in system, is warming up to 40-80oC, is incubated 12-24 hour.Wherein, the structure of described dicarboxylic acid compound is：, wherein R is as defined above and states.Wherein, described dicarboxylic acid compound select oxalic acid, third
Diacid, succinic acid, malic acid.These dicarboxylic acid compounds are commercially available and can be without being further purified.
The present invention provide including formula（1）In polymer with thiadiazoles drone salt construction unit as leveling agent plating
Composition can at least improve leveling performance than a lot of conventional acid copper plating compositions so as to suitable for the electroplates in hole and
Blind hole filling is while electroplating technology.
Acid copper plating can be by method known to any prior art and document come electro-coppering in substrate with composition
Metal.Typically, using conventional electroplating device by conventional electroplating process incoming call copper-plated metal.These electroplating process are all
Known in the field.Current density and electrode surface current potential can change with specifically substrate to be plated.In general, anode and
Cathode-current density can be in 0.1-10A/dm2In the range of change, preferred current density is in 0.2A/dm2To 3A/dm2, typically
For 2A/dm2.Maintain temperature of electroplating solution scope be from 18-35oC, preferred range be from 23-25oC.
The present invention is showed according to above-mentioned theory and practical application, has been designed and synthesized a kind of with thiadiazoles drone salt structure list
Used as the leveling agent of sour copper electroplating bath, for acid electroplating, blind hole filling is not in space to the polymer of unit, and amount of recess
With respect to existing conventional planarization agent（As Janus green）Significantly reduce, the electroplates in hole shows good dispersibility, y/x value
0.8 is all higher than, can more ideally be realized the electroplates in hole and blind hole is filled while electroplating technology.
Description of the drawings
The detailed description that non-limiting example is made with reference to the following drawings by reading, the further feature of the present invention,
Objects and advantages will become more apparent upon：
Fig. 1 is the nucleus magnetic hydrogen spectrum figure of 1 polymer P 1 of embodiments of the invention.
The space schematic diagram that Fig. 2 is filled for blind hole.
Fig. 3 fills amount of recess schematic diagram for blind hole.
Fig. 4 is the y/x value schematic diagram of through hole.
Fig. 5 is blind for the blind hole filling effect of acid copper plating liquid of the present invention with the polymer P 1 of embodiment 1 as leveling agent
Hole filling effect figure.
The electroplates in hole effect of acid copper plating liquid of the Fig. 6 for the present invention with the polymer P 1 of embodiment 1 as leveling agent
Figure.
Specific embodiment
The present invention is described in detail with specific embodiment below in conjunction with the accompanying drawings.Following examples will be helpful to this area
Technical staff further understand the present invention, but the invention is not limited in any way.It should be pointed out that to the general of this area
For logical technical staff, without departing from the inventive concept of the premise, some deformation and improvement can also be made.These belong to
Protection scope of the present invention.
Embodiment 1
The polymer with thiadiazoles drone salt construction unit is present embodiments provided, its structural formula is as shown in table 1（Wherein, n
It is the integer more than or equal to 2）, its synthetic route is as follows：
Table 1：1 structural formula of polymer P that embodiment 1 is provided
The preparation method of polymer P 1, comprises the steps：
Step 1, the synthesis of 2,5- diaminourea thiadiazoles
The structural formula of 2,5- diaminourea thiadiazoles is
Its detailed preparation method is shown in document《 Johnson FA; Saliu AA; Amudat L. Zn(II) complex
with N- and S-donor ligand: synthesis and biological studies. Journal of
Chemical and Pharmaceutical Research. 4(3), 1511-1518 (2012) 》.
Step 2, the synthesis of polymer P 1
Under nitrogen protection, by 2,5- diaminourea thiadiazoles（2.32g, 20mmol）, 1,3- malonic acid（2.08g,
20mmol）, deionized water（2mL）It is added in pressure bottle, is warming up to 180 DEG C（Can be 150-200oArbitrary value in C）Reaction
8h.Reactant liquor is naturally cooled to room temperature.By dimethyl suflfate（7.57g, 60mmol）And methyl alcohol（20mL）It is added to pressure bottle
In, it is warming up to 60 DEG C（Can be 40-80oArbitrary value in C）Reaction 16h.Reactant liquor is naturally cooled to room temperature.Vacuum distillation is gone
Except first alcohol and water, polymer P 1 is obtained.1H NMR (400 MHz, CDCl3), 3.86-3.79 (s, 2H), 1.27 (t,J= 7.0 Hz, 9H). Anal. calcd for (C8H11N4O2S)n: C 42.28, H 4.88, N 24.65;
found: C 42.43, H 4.98, N 24.76.The nucleus magnetic hydrogen spectrum figure of polymer P 1 is shown in Figure 1.Will be molten for polymer P 1
Solution is in 1 liter of water, with 20% dilute sulfuric acid adjustment solution ph to about 7 as leveling agent, standby.
Embodiment 2
Product in table 2 is prepared in the same manner as in Example 1.The elementary analysis result of the product collects
In table 2.
Table 2：The elementary analysis result of P2-P9
Embodiment 3
By mixing 180g/L as the cupric sulfate pentahydrate in copper source, 60g/L sulfuric acid, 50ppm chlorion, poly- two sulphur two of 1ppm
Propane sulfonic acid sodium and 400ppm PEG20000 are obtained copper electroplating liquid.Reaction in plating solution also containing 5mL/L embodiment 1 is produced
Thing.
Embodiment 4
Substantially different copper electroplating liquids are prepared according to embodiment 3, except content is the embodiment 2 of 5mL/L used in which
Each product.
Embodiment 5（Comparative example）
Substantially different copper electroplating liquids are prepared according to embodiment 3, except content is the Janus green of 5ppm used in which
（Janus Green）As leveling agent.
Embodiment 6
Each plating solution above-mentioned is used in 100 μm of through hole and aperture with 2mm thickness and diameter 0.3mm and hole depth 70
μm blind hole printed wiring board on copper electroplating layer.Plating test is carried out in Haring cell.Bath temperature is 24oC.Each coating bath
Apply 2A/dm2Current density 50 minutes.Space of the plating result with reference to shown in Fig. 2,3,4, amount of recess, the evaluation side of x/y value
Method is carried out.The blind hole filling effect of the acid copper plating liquid being illustrated in figure 5 with P1 as leveling agent, its tight, amount of recess for-
2 microns.The electroplates in hole result of the acid copper plating liquid being illustrated in figure 6 with P1 as leveling agent.All electroplating effects such as 3 institute of table
Show.
Table 3：With P1-P9, the electroplating effect of the acid copper plating liquid of the Janus green as leveling agent of comparative example
Using the present invention the polymer with thiadiazoles drone salt construction unit for leveling agent copper electroplating liquid, blind hole fill
All there is not space, and amount of recess is respectively less than and Janus green is used as the comparative example result of leveling agent.The electroplates in hole table
Reveal good dispersibility, y/x value is all higher than 0.8.
In sum, the leveling agent that the present invention is provided, with thiadiazoles drone salt construction unit, for acid copper plating, body
Reveal good the electroplates in hole and blind hole is filled while electroplating effect.
Although present disclosure has been made to be discussed in detail by above preferred embodiment, but it should be appreciated that above-mentioned
Description is not considered as limitation of the present invention.After those skilled in the art have read the above, for the present invention's
Multiple modifications and substitutions all will be apparent.Therefore, protection scope of the present invention should be limited to the appended claims.
Claims (5)
1. a kind of leveling agent for acid copper plating, it is characterised in that the leveling agent be with thiadiazoles drone salt construction unit
Polymer, its structural formula such as formula（1）Shown：
Wherein, selected from the organic group of 0-10 carbon atom, n is the integer not less than 2 to R.
2. the leveling agent of acid copper plating is used for as claimed in claim 1, it is characterised in that R is selected from the alkane of 2-8 carbon atom
Epoxide.
3. the leveling agent of acid copper plating is used for as claimed in claim 1, it is characterised in that R is selected from the alkane of 0-5 carbon atom
Base.
4. the leveling agent of acid copper plating is used for as claimed in claim 1, it is characterised in that R contains selected from 1-4 carbon atom
The alkyl of hydroxyl.
5. a kind of purposes of the leveling agent according to any one in claim 1-4, it is characterised in that the leveling agent is used for
Through hole in printed wiring board and blind hole filling are while electroplate.
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| CN105839151B (en) * | 2016-04-19 | 2018-08-21 | 电子科技大学 | A kind of plating agent of HDI plate electrolytic copper plating baths for copper-connection and electrolytic copper plating bath |
| CN105951137B (en) * | 2016-05-23 | 2017-12-01 | 中国广州分析测试中心 | A kind of blind buried via hole copper plating solution of HDI laminated plates |
| CN107217306B (en) * | 2017-05-19 | 2023-07-07 | 湖州三峰能源科技有限公司 | Chemical composition of polycrystalline silicon wafer acid texturing optimizing agent and application thereof |
| CN107326348A (en) * | 2017-07-24 | 2017-11-07 | 电子科技大学 | A kind of method and related chemistry copper plating bath that core inductance quality value is lifted based on chemical plating Porous Cu |
| CN111155153B (en) * | 2020-02-19 | 2021-06-08 | 广州三孚新材料科技股份有限公司 | Copper electroplating solution and copper electroplating method |
| CN113737232B (en) * | 2021-11-08 | 2022-01-11 | 深圳市板明科技股份有限公司 | Circuit board through hole copper electroplating leveling agent and application and preparation method thereof |
| CN114574911B (en) * | 2022-04-28 | 2022-07-19 | 深圳市板明科技股份有限公司 | Electroplating process for through hole of circuit board with high thickness-diameter ratio |
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| JP4973829B2 (en) * | 2004-07-23 | 2012-07-11 | 上村工業株式会社 | Electro copper plating bath and electro copper plating method |
| US20070170066A1 (en) * | 2006-01-06 | 2007-07-26 | Beaudry Christopher L | Method for planarization during plating |
| JP5558675B2 (en) * | 2007-04-03 | 2014-07-23 | ローム・アンド・ハース・エレクトロニック・マテリアルズ，エル．エル．シー． | Metal plating composition |
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